scholarly journals Real-time, controlled OH-initiated oxidation of biogenic secondary organic aerosol

2012 ◽  
Vol 12 (3) ◽  
pp. 8183-8224 ◽  
Author(s):  
J. G. Slowik ◽  
J. P. S. Wong ◽  
J. P. D. Abbatt
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Aerosol Formation ◽  
Organic Mass ◽  
Ambient Aerosol ◽  
Atmospheric Processing

Abstract. The chemical complexity of atmospheric organic aerosol (OA) requires novel methods for characterization of its components and description of its atmospheric processing-induced transformations. We present the first field deployment of the Toronto Photooxidation Tube (TPOT), a field-deployable flow reactor for the controlled exposure of ambient aerosol to OH radicals. The system alternates between sampling of (1) unreacted ambient aerosol, (2) aerosol subjected to a ~4 °C temperature increase, and (3) aerosol that is both heated and oxidized by OH. This allows both characterization of the aging process and classification of aerosol in terms of its volatility and reaction-based properties. Summertime measurements by an aerosol mass spectrometer coupled to the TPOT were performed in the remote forest of Western Canada, resulting in aerosol dominated by biogenic secondary organic aerosol. Volatilization resulted in an approximately 10 to 25% decrease in organic mass and resulted in a slight increase in oxygenation. OH oxidation resulted in a further organic mass decrease (additional ~25%) and yielded an aerosol with O:C values comparable to those characteristic of low volatility, highly oxygenated OA. Most OH-induced changes occurred within the equivalent of ~3 days of atmospheric processing, with further reactions generally proceeding at a greatly reduced rate. Positive matrix factorization (PMF) analysis of the TPOT data yielded five factors. One factor is related to primary biomass burning organic aerosol, while the others describe oxygenated organic aerosol (OOA) components in terms of reactivity and volatility: (1) volatile and reactive; (2) non-volatile and reactive; (3) non-volatile and reactive early-generation product; (4) non-volatile and non-reactive product. This PMF classification of aerosol components directly in terms of reactivity and volatility is enabled by the TPOT-modulated perturbation of aerosol composition, and is not otherwise accessible. The particle-phase reaction end products have mass spectra similar to the low-volatility oxygenated organic aerosol (LV-OOA) factors widely reported in the literature, providing supporting evidence for aged organic aerosol formation from OH-driven oxidation processes.

scholarly journals Real-time, controlled OH-initiated oxidation of biogenic secondary organic aerosol

2012 ◽  
Vol 12 (20) ◽  
pp. 9775-9790 ◽  
Author(s):  
J. G. Slowik ◽  
J. P. S. Wong ◽  
J. P. D. Abbatt
Keyword(s):  
Temperature Increase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Uv Exposure ◽  
Oh Radicals ◽  
Organic Mass ◽  
Ambient Aerosol ◽  
Atmospheric Processing

Abstract. The chemical complexity of atmospheric organic aerosol (OA) requires novel methods for characterization of its components and description of its atmospheric processing-induced transformations. We present the first field deployment of the Toronto Photooxidation Tube (TPOT), a field-deployable flow reactor for the controlled exposure of ambient aerosol to OH radicals. The system alternates between sampling of (1) (unreacted) ambient aerosol, (2) aerosol exposed to UV light and subjected to a ~4 to 10 °C temperature increase, and (3) aerosol that is oxidized by OH (in addition to the aforementioned UV exposure/temperature increase). This allows both characterization of the aging process and classification of aerosol in terms of its volatility and reaction-based properties. Summertime measurements by an aerosol mass spectrometer coupled to the TPOT were performed in the remote forest of western Canada, resulting in aerosol dominated by biogenic secondary organic aerosol. Volatilization/UV exposure resulted in an approximately 10 to 25% decrease in organic mass and resulted in a slight increase in oxygenation. OH oxidation resulted in a further organic mass decrease (additional ~25%) and yielded an aerosol with O:C values comparable to those characteristic of low volatility, highly oxygenated OA. Most OH-induced changes occurred within ~3 day-equivalents of atmospheric processing, with further reactions generally proceeding at a greatly reduced rate. Positive matrix factorization (PMF) analysis of the TPOT data yielded five factors. One factor is related to primary biomass burning organic aerosol, while the others describe oxygenated organic aerosol (OOA) components in terms of reactivity and volatility: (1) volatile and reactive; (2) non-volatile and reactive; (3) non-volatile and reactive early-generation product; (4) non-volatile and non-reactive product. This PMF classification of aerosol components directly in terms of reactivity and volatility is enabled by the TPOT-modulated perturbation of aerosol composition, and is not otherwise accessible. The particle-phase reaction end products have mass spectra similar to the low-volatility oxygenated organic aerosol (LV-OOA) factors widely reported in the literature, providing supporting evidence for aged organic aerosol formation from OH-driven oxidation processes.

scholarly journals Secondary organic aerosol formation from OH-initiated oxidation of <i>m</i>-xylene: effects of relative humidity on yield and chemical composition

2019 ◽  
Vol 19 (23) ◽  
pp. 15007-15021 ◽  
Author(s):  
Qun Zhang ◽  
Yongfu Xu ◽  
Long Jia
Keyword(s):  
Relative Humidity ◽  
Mass Spectrometer ◽  
Secondary Organic Aerosol ◽  
Carbon Number ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Aerosol Formation ◽  
Liquid Chromatograph

Abstract. The effect of relative humidity (RH) on secondary organic aerosol (SOA) formation from the photooxidation of m-xylene initiated by OH radicals in the absence of seed particles was investigated in a Teflon reactor. The SOA yields were determined based on the particle mass concentrations measured with a scanning mobility particle sizer (SMPS) and reacted m-xylene concentrations measured with a gas chromatograph–mass spectrometer (GC-MS). The SOA components were analyzed using a Fourier transform infrared (FTIR) spectrometer and an ultrahigh-performance liquid chromatograph–electrospray ionization–high-resolution mass spectrometer (UPLC-ESI-HRMS). A significant decrease was observed in SOA mass concentration and yield variation with the increasing RH conditions. The SOA yields are 14.0 %–16.5 % and 0.8 %–3.2 % at low RH (14 %) and high RH (74 %–79 %), respectively, with the difference being nearly 1 order of magnitude. Some of the reduction in the apparent yield may be due to the faster wall loss of semi-volatile products of oxidation at higher RH. The chemical mechanism for explaining the RH effects on SOA formation from m-xylene–OH system is proposed based on the analysis of both FTIR and HRMS measurements, and the Master Chemical Mechanism (MCM) prediction is used as the assistant. The FTIR analysis shows that the proportion of oligomers with C-O-C groups from carbonyl compounds in SOA at high RH is higher than that at low RH, but further information cannot be provided by the FTIR results to well explain the negative RH effect on SOA formation. In the HRMS spectra, it is found that C2H2O is one of the most frequent mass differences at low and high RHs, that the compounds with a lower carbon number in the formula at low RH account for a larger proportion than those at high RH and that the compounds at high RH have higher O : C ratios than those at low RH. The HRMS results suggest that the RH may suppress oligomerization where water is involved as a by-product and may influence the further particle-phase reaction of highly oxygenated organic molecules (HOMs) formed in the gas phase. In addition, the negative RH effect on SOA formation is enlarged based on the gas-to-particle partitioning rule.

scholarly journals Secondary organic aerosol formation from biomass burning emissions

2019 ◽  
Author(s):  
Christopher Y. Lim ◽  
David H. Hagan ◽  
Matthew M. Coggon ◽  
Abigail R. Koss ◽  
Kanako Sekimoto ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Secondary Organic Aerosol ◽  
Total Concentration ◽  
Organic Aerosol ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Atmospheric Aging ◽  
Aerosol Mass ◽  
Photochemical Aging ◽  
Organic Gases

Abstract. Biomass burning is an important source of aerosol and trace gases to the atmosphere, but how these emissions change chemically during their lifetimes is not fully understood. As part of the Fire Influence on Regional and Global Environments Experiment (FIREX 2016), we investigated the effect of photochemical aging on biomass burning organic aerosol (BBOA), with a focus on fuels from the western United States. Emissions were sampled into a small (150 L) environmental chamber and photochemically aged via the addition of ozone and irradiation by 254 nm light. While some fraction of species undergoes photolysis, the vast majority of aging occurs via reaction with OH radicals, with total OH exposures corresponding to the equivalent of up to 10 days of atmospheric oxidation. For all fuels burned, large and rapid changes are seen in the ensemble chemical composition of BBOA, as measured by an aerosol mass spectrometer (AMS). Secondary organic aerosol (SOA) formation is seen for all aging experiments and continues to grow with increasing OH exposure, but the magnitude of the SOA formation is highly variable between experiments. This variability can be explained well by a combination of experiment-to-experiment differences in OH exposure and the total concentration of non-methane organic gases (NMOGs) in the chamber before oxidation, measured by PTR-ToF-MS (r2 values from 0.64 to 0.83). From this relationship, we calculate the fraction of carbon from biomass burning NMOGs that is converted to SOA as a function of equivalent atmospheric aging time, with carbon yields ranging from 24 ± 4 % after 6 hours to 56 ± 9 % after 4 days.

scholarly journals In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

2015 ◽  
Vol 15 (21) ◽  
pp. 30409-30471 ◽  
Author(s):  
B. B. Palm ◽  
P. Campuzano-Jost ◽  
A. M. Ortega ◽  
D. A. Day ◽  
L. Kaser ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Ambient Air ◽  
Organic Aerosol ◽  
Pine Forest ◽  
Oxidation Products ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Photochemical Aging

Abstract. Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. Several recently-developed instruments quantified ambient semi- and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a PTR-TOF-MS. An SOA yield of 24–80 % from those compounds can explain the observed SOA, suggesting that these typically unmeasured S/IVOCs play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Our measurements help clarify the magnitude of SOA formation in forested environments, and demonstrate methods for interpretation of ambient OFR measurements.

scholarly journals Gaseous products and secondary organic aerosol formation during long term oxidation of isoprene and methacrolein

2015 ◽  
Vol 15 (6) ◽  
pp. 2953-2968 ◽  
Author(s):  
L. Brégonzio-Rozier ◽  
F. Siekmann ◽  
C. Giorio ◽  
E. Pangui ◽  
S. B. Morales ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Solar Spectrum ◽  
Organic Aerosol ◽  
Product Distribution ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Experimental Conditions ◽  
Gaseous Products ◽  
Oxidation Rates

Abstract. First- and higher order-generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Significant oxidation rates have been maintained for up to 7 h, allowing the study of highly oxidized products. Gas-phase product distribution and yields were obtained, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation has also been investigated. SOA mass yields from previous studies show large discrepancies. The mass yields obtained here were consistent with the lowest values found in the literature, and more specifically in agreement with studies carried out with natural light or artificial lamps with emission similar to the solar spectrum. Differences in light source are therefore proposed to explain partially the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. There is a high degree of similarity between the SOA mass spectra from isoprene and methacrolein photooxidation, thus strengthening the importance of the role of methacrolein in SOA formation from isoprene photooxidation under our experimental conditions (i.e., presence of NOx and long term oxidation). According to our results, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.

scholarly journals Secondary organic aerosol formation from smoldering and flaming combustion of biomass: a box model parametrization based on volatility basis set

2019 ◽  
Author(s):  
Giulia Stefenelli ◽  
Jianhui Jiang ◽  
Amelie Bertrand ◽  
Emily A. Bruns ◽  
Simone M. Pieber ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Secondary Organic Aerosol ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Box Model ◽  
Basis Set ◽  
Model Parameters ◽  
Oh Radicals ◽  
Smog Chamber ◽  
Aerosol Formation

Abstract. Box model simulations based on the volatility basis set (VBS) approach were used to assess secondary organic aerosol (SOA) precursors and volatility distributions from residential wood combustion. Emissions were sampled from three different residential stoves at different combustion conditions (flaming vs. smoldering-dominated), aging temperatures (−10 °C, 2 °C and 15 °C), and emission loads, then exposed to hydroxyl (OH) radicals in a smog chamber. Primary emissions of SOA precursor compounds, organic aerosol and their evolution during aging in the smog chamber were monitored by a comprehensive suite of gas and particle instrumentation, including a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). SOA precursors were classified according to their chemical composition and the identification of the nature of the precursors revealed useful to better constrain model parameters, in particular SOA production rates and molecular characteristics of the condensable gases formed. The general aim of the model was the determination of the parameters describing the volatility distributions of the oxidation products from the different chemical classes considered and their temperature dependence. Novel parameterization methods based on a genetic algorithm (GA) approach allowed estimation of precursor class contributions to SOA and evaluation of the effect of emission variability on SOA yield predictions. Significant differences were observed in the gas-phase composition between smoldering and flaming emissions. Smoldering phase emissions were dominated by oxidized VOCs with less than six carbon atoms family (OVOCc 

scholarly journals Secondary inorganic aerosols in Europe: sources and the significant influence of biogenic VOC emissions, especially on ammonium nitrate

2017 ◽  
Vol 17 (12) ◽  
pp. 7757-7773 ◽  
Author(s):  
Sebnem Aksoyoglu ◽  
Giancarlo Ciarelli ◽  
Imad El-Haddad ◽  
Urs Baltensperger ◽  
André S. H. Prévôt
Keyword(s):  
Ammonium Nitrate ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Anthropogenic Sources ◽  
Anthropogenic Source ◽  
Oh Radicals ◽  
Aerosol Formation ◽  
Air Quality Model ◽  
Inorganic Nitrate ◽  
Inorganic Aerosol

Abstract. Contributions of various anthropogenic sources to the secondary inorganic aerosol (SIA) in Europe as well as the role of biogenic emissions on SIA formation were investigated using the three-dimensional regional model CAMx (comprehensive air quality model with extensions). Simulations were carried out for two periods of EMEP field campaigns, February–March 2009 and June 2006, which are representative of cold and warm seasons, respectively. Biogenic volatile organic compounds (BVOCs) are known mainly as precursors of ozone and secondary organic aerosol (SOA), but their role on inorganic aerosol formation has not attracted much attention so far. In this study, we showed the importance of the chemical reactions of BVOCs and how they affect the oxidant concentrations, leading to significant changes, especially in the formation of ammonium nitrate. A sensitivity test with doubled BVOC emissions in Europe during the warm season showed a large increase in secondary organic aerosol (SOA) concentrations (by about a factor of two), while particulate inorganic nitrate concentrations decreased by up to 35 %, leading to a better agreement between the model results and measurements. Sulfate concentrations decreased as well; the change, however, was smaller. The changes in inorganic nitrate and sulfate concentrations occurred at different locations in Europe, indicating the importance of precursor gases and biogenic emission types for the negative correlation between BVOCs and SIA. Further analysis of the data suggested that reactions of the additional terpenes with nitrate radicals at night were responsible for the decline in inorganic nitrate formation, whereas oxidation of BVOCs with OH radicals led to a decrease in sulfate. Source apportionment results suggest that the main anthropogenic source of precursors leading to formation of particulate inorganic nitrate is road transport (SNAP7; see Table 1 for a description of the categories), whereas combustion in energy and transformation industries (SNAP1) was the most important contributor to sulfate particulate mass. Emissions from international shipping were also found to be very important for both nitrate and sulfate formation in Europe. In addition, we also examined contributions from the geographical source regions to SIA concentrations in the most densely populated region of Switzerland, the Swiss Plateau.

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

2009 ◽  
Vol 43 (21) ◽  
pp. 3440-3444 ◽  
Author(s):  
Roger L. Tanner ◽  
Kenneth J. Olszyna ◽  
Eric S. Edgerton ◽  
Eladio Knipping ◽  
Stephanie L. Shaw
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Ambient Aerosol ◽  
Acid Catalyzed ◽  
Secondary Organic Aerosol Formation
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